Arylphosphate compounds



United States PatentO 2,982,686 ARYLPHOSPHATE COMPOUNDS Richard R.Whetstone and Alan R. Stiles, Modesto, Calif., assignors to Shell OilCompany, New York, N.Y a corporation of Delaware No Drawing. Filed Dec.23, 11957, star. No. 704,321; 18 Claims. Cl. 167-30) This inventionrelates to novel eomplex-aryl compounds which contain phosphorus and tothe employmentwof these compounds as insecticides. phosphorus-containingcompounds have become important in recent years because of their'potencyas insecticides.

For example, Stiles, Us. 2,685,552 (Shell Development Certain organicresidual toxicity. The need for potent phosphorus-com taininginsecticides manifesting extended residual toxicity has thus becomeincreasingly manifest. The novel insecticides of the present inventionsatisfy this urgent need without sacrificing the characteristic potencyand other advantages of these knownorganic-phosphorus insec- .ticides.The principal object of the present invention is then to provide organicphosphorus containing insecticidal compounds evidencing high initialpotency, ex- -tended residual toxicity, yet which are relativelyinexpensive -to synthesize and formulate.

Another object of the present invention is to provide insecticidalcompositions containing these compounds.

,.Yet another object .of the present invention is to provide a method ofcombating insects comprising essentially contacting insects withthese/novel compounds.

Other objects, features and advantages of the present invention will beapparent from the following description read in conjunction with theappended claims.

The new and novel compounds encompassed by the present invention may berepresented by the following structural formula:

a O CH: O (RO)r O( =GH( J-0R wherein R is an aralkyl or aryl radical.When R is an ,a'r-alkyl radical the alkyl portion may contain 1-5 carbonatoms and is a branched or straight chain. The alkyl portion of thear-a-lk-yl group is preferably methyl. When R is an aralk-yl group thearyl portion. of the molecule may be aphenyl or tolyl group. The arylportion of the molecule may be unsubstituted or substituted with ana'lkoxy group, particularly methoxy group. R is a lower alkyl radicalwith may contain l-5 carbon atoms. Methyl is preferred.- Specificexamples of compounds encompassed by the present invention are: dimethyllmethyl-2-(5-phenylpentyloxycarbonyl) vinyl phosphate, dimethyl 1methyl-Z-(2-benzy1oxyethoxycarbonyl) vinyl phosphate, dimethyl1-methyl-2 (tolyloxycarbonyDvinyl phosphate, dimethyl 1 methyl 2(phenoxyc'arbonyly vinyl phosphate, Z-(benzyloxycarbonyl)-methylvinyldimethyl phosphate, 2 (p-methoxyphenoxycarbonyl) -1- methylvinyldimethyl phosphate, diethyl 1-methyl-2-(ptolyloxycarbonyl) vinylphosphate, 1 methyl 2-(phen- .ethoxycarbonyl)viuyl diprOPYl phosphate,l-(p-methoxy- ,benzyloxycarbonyl)-l methylvinyl dimethyl phosphate,

Patented May 2, 1961 dimethyl 2-( alpha-methyl-benzyloxycarbonyl)-'l-methyl'- vinyl phosphate, dimethyl 1-methyl-'2'-(2-phenoxyethoxycar-bonyl')vinyl phosphate, and1-methy12-'(=5-p'henylpentyloxycarbonynvinyl dipentyl phosphate. -Othercompou'nds of the present invention are-hereinafter described. 1 1

The novel compounds of the present invention can be prepared by any ofthe methods known in the art for synthesizing compounds of this generalcharacter. If desired compounds of the present invention may be preparedby reacting trialkyl' phosphite with the appropriate arylhaloacetoacetate as shown in the following general formula:

In this equation R is an a'ralkyl or aryl radical 'asdefined above andR" isa lower alkyl radical as defined above.

The preparations of the specific compounds of the present invention areillustrated .by the following examples: e

I. DIMETHY-L l-METHYL-Z-(PHENOXYCARBON- YL)VINYL PHOSPHATE 59 g. (0.475mole) (about 10% excess) of trimethyl phosphite were added at -100 over1 hour to 92 g. (0.433 mole) of phenyl 2-clrloroacetoacetate. Themixture was heated -for 1 hour at 110 then at 8 )/170 mm. for 1 hour.Total cold trap contents: 19.5 g, CH Cl (89.1% of theory), f f

This material was stripped in a molecular still and then distilled to.give 19 g. (100405 0.001 mm.) and a'residue of 99 g. The residue wasdistilled yielding 84.0 g'. (l10-1l2/0.001 mm.) and a residue of 15.0 g.

The distillate of 84 g. (67.7% theory) analyzed as follows:

vFound Gale.

. K Oo HHM) C 50.2 "50.3 H 5.3 5.2 ("I a None None P me Y 10.82

It will be understood that the corresponding .diethyh, dipropyl,dibutyland dipentyl vinyl phosphate may be prepared by employingtriethyl-, tripropyL, tributylor tri pentyl phosphite respectively.

II. 2-( BENZYLOXYCARBONYL) -l-METHYLVINYL DIMETHYL PHOSPHATE I ll 011.0;oc=oHo 0 om+ornox V 3 with stirring. The temperature rose during theaddition to 120 and after the addition the reaction was held at 120-125"for one hour. It was then stripped to 100 at Ihouse vacuum pressure. Thecold trap contents weighed 29 g., B.P. 24. i

This reaction product was distilled on the. molecular still at 135-l45at 0.000 1 mm. to give 103 g., n F 1.5067. The residue was distilled at140145/0.0001 mm. to give 63 g., n 3 1.5072, and a residue 11 15079, 12g. which was discarded.

The distillate of 63 g. (55% theory) analyzed as follows:

Emma Cale. m n a) III. 2-(p-METHOXYPHENOXYCARBONYL)-1- A METHYLVINYLDIMETI- IYL PHOSPHATE II II 30 OCCHClCOH34-(CHaO)aP- 70 g. ofp-methoxyphenyl 2-chloroacetoacetate were placed in a 300 cc. roundbottom 3-necked flask fitted with dropping .funnel, mechanical stirrer,and 4-tube carrying a thermometer and reflux condenser attached to acold trap for collection of evolved CHgCl 42 g. of trl the flask wasfurther heated to 105 and stirred for an additional 1.5 hours. The coldtrap contained 12 g., B.P. 23 C. The reaction mixture was stripped to80/7 mm. and the residue stripped on the molecular still at .0005 mm. toyield 80g; of residue. The residue from stripping on the molecular stillwas distilled at 115 120/.0005 mm. to yield a distillate which was savedand a residue which was distilled on the molecular still at158-160/.0005 mm. to give 49 g. distillate and 4 g. of residue which wasdiscarded. The distillates were combined and redistilled on themolecular still at 140/ 0.0005 mm. Yield 74.5%.

Thedistillate analyzed as follows:

Found Cale. (C HnP 1) IV. DIMETHYL l-METHYL-Z-(p-TOLYLOXY-CARBONYL)VINYL PHOSPHATE CHI OGOCHOICOCH: OCOCH= CH1 H] 73 g. ofp-tolyl2-chloroacetoacetate were heated to C. in a 300' cc. round bottomS-necked flask fitted with dropping funnel; stirrer and 4-tube..fittedwith thermometer and condenser to which is attached a cold trap forcollection of methyl chloride. 42 cc. trimethyl phosphite were addeddropwise. The reaction was exothermic and the temperature of thereaction mixture rose from 80 to 120;it was then cooled'to 80. anditrose again to After complete addition (40 minutes) the reactionwas'stirredan'additional 2"hours at a temperature of 1059.. It was thenstripped to 50.K;T. an'd'7 mm. pressure. f I

The reaction mixture was then stripped to 105 K .T. and 0.02 mm.pressure,. and distilled on the'molecularstill after being stripped-at55/.0005 mm; to" giye'l' g. of distillate which was discarded and adark' green residue. This residuewas .distiled at 140/ .0005 mm; to give80 g. (83% theory of chart'reuse-colored distillate and 8 g. of darkgreen colored residue, the latter of which was discarded. Thechartreuse-colored distillate was redistilled on the molecular still at-1l8'and 0.0005 mm. to give 66 g. of fluorescent yellow distillate;Yield 68.2%.

The distillate analyzed asfollowsz,

Found Cale.

( u n a) C 53. 7 52. 00 H 5. 5 5. 71 01 1, 2 0 P 9. 7 10. 32

It will be understood that the corresponding diethyl-, dipropyl-,dibutyl-, and dipentyl vinyl phosphate may be prepared by employingtriethyl-, tripropyl-, tributyl-, or tripentyl phosphite respectively. j

.V. DI METHYL l-METHYL-Z-(PHENETHOXY- CARBONYL) -VINYL PHOSPHATE thatthe temperature was maintained (35 minutes requiredfor addition) andthen the reaction was maintained at 80 by external heating for 45minutes and then at for an additional 45 minutes. The reaction mixturewas stripped to 50/ .6 mm. The cold trap contained 16 g.

of material boiling below 0". The reaction mixture was then stripped onthe molecular still at 55'58/ .0005 mm. From 109 g. crude product therewas obtained a distillate of 3 g. which was discarded and a residue of103' g. This residue was distilled on the molecular still at -5/ 0.0005mm. yielding 99 g. of a pale yellow distillate with greenishfluorescence and 4 g. of-dark green residue which was discarded. Yield88.5%. The distillate analyzed as follows:

It will be understood that the corresponding diethyl-, dipropyl-,dibutyl-, and dipentyl vinyl phosphate may be prepared by employingtriethyl-, tripropyltributylor tripentyl phosphite respectively.

VII. DIMETHYL 2-(A-METHYLBENZYLOXY CARBONYL) -1-METHYLVINYL PHOSPHATEFound Cale. (1:11.19 5 (a) H (OHHIBPOO GH;COCH1COOC|H5++H0++ 53.8 53.45

6.0 6.09 ,nnmhoz'l is g 87 orrrooourooo -+ormorr It will be understoodthat the corresponding diethyl E dipropyl-, dibutyland dipentyl vinylphosphate maybe prepared by employing triethyl-, tripropyl-, a,tripentyl phosphite, respectively. V i (b) H omoocflroooh VI.2-(p-METHOXYBENZYLOXYCARBONYL)- 1- OH +sO,C1,-

METHYLVINYL DIMETHYL PHOSPHATE O I OHr0noHnGHr+(CHr0)aP- GHiOOOHGlCOOt JO l C +SOI+HCI C CHzO1+ onrot lon=h (c) &

. H P.- 3H o i t a g a 0 on. n Anisyl 2-chloroacetoacetate, 85 g. (0.33mole) was 9' stirred and heated to 80 .C. in a 300 cc. round bottom H,S-necked flask, fitted with dropping funnel, mechanical stirrer and a4-tube carrying a'therrnometer and a ren flux condenser attached to aDry Ice-acetone cold trap. Reactwn i e 1 Q Product "D Tlfirnethyl phosphit e, 47 cc. (10% excess) was added 34 m 'Methylbenlyl acefioacetatedropwise to the stirred liquid. The reaction'was Iexo- 5-0 153-0 8- ml): Po e nt 90 thermic, so the heating mantle was removed during ap- Iml bottomed a e uippe v ith, .S ITIe IQ proximately /3 of the additionof the trimethyl phos- 4o r ux d Q nd n X i o n d to aw te t p) phite,and the temperature was maintained between 80 ppin l e an h mom m ers she li l i iand 100. As the temperature -showed signs of falling Then z z03011101) Were added p' heating was resumed during the'last portion ofthe addi Wise maintaining the mper ture at 10-15 during V2 tion of thetrimethyl phosphite. Addition required hour- The reaction X was allowedto Stand Overminutes. The reaction mixture was then heated to 120-llight- The lemon-colored liquid Was Stirred at 125 and then stirred anadditional hour to obtain comfor 1 hour, P p out y house Vacuum for 1110111 at plete reaction. Cold trap contents 14 g. The reaction was n hy yfor 15 then stripped at the house vacuum and 1 g. of materialminutes- Hs )a [1101) Was added pcollected in the cold trap. The residuewas transferred Wise to the Stirred reaction mixture at Such a i a to adistillation kettle (200 cc.) The residue was stripped the temperaturewas maintained t 5 during the'45 w' p 130 mm pressure and 19 ofmateyial50 minutes required. The mixture was allowed to stand n 1.4095, B.P.32-37/6 mm. was collected. The Overnight remaining 96 g. of crudeproduct was stripped onithe' Thelmixtule'lwas newiheated and stirred at75n800f01' molecular still at /.0005 The. 5 g. distillate was 1 hour andthen the house vac pp for lhour at the discarded and the residue of 9was distill ed o n 1 same temperature. The trap contained 35.0 g. of CHCI molecular still at 13s-142/.000s mm. The yield or di of y)Thelemon-colored q i was pp tilled material was 77 g. with a residue of8 g. which was for 2 hours at and then Passed discarded. This distillatewas redistilled on the molecuthrough the molecular Still at 80/10 5 ThisP lar still at -110 to give a distillate 15 g., whichwas uct weighed -0(mo and was distilled at discarded after analysis, and a residue of 58g, (yield 145-15'0/10"5mm- Yielding 131-0 0f lemen-eelored 52.6%) whichanalyzed as follows: i 50 Oi ("n 1- 9 1 Yield 595%) which was .alyzed asfollows:

Found 1 0810(Cr4HmP07) Distillate Residue 5 5 Found Calc.(O Hi 0 P) 52.6.50.91 52.3 53.5 6.4 5.80 6.1 6.04 .6 o I 9.9 9.9 1 9.38 Y

It will be understood that the corresponding diethyl-, dipropyl-,dibutyl-, and dipentyl vinyl phosphate may be 7 VIII. DIMETHYLl-METHYL-Z- (Z-PHENOXY- ETHOXYCARBONYL)VINYL PHOSPHATE CHQCOCHxCOO031140 +B Ola CHCOCHCIOOOCHHAO +SOn+HCl CHaC O CHCICO O CZ AO orno=cnooo0.21.0

2-phenoxyethyl acetoacetate (78 g.; 0.352 mol) was placed in around-bottom flask equipped with stirrer, reflux condenser and additiontube. The stirrer was started and the mixture cooled to 10. temperatureat 10l5 there was added during the course 015% hour 45.0 g. (27cc.;.0.333 mol) of SO Cl After completing the addition the mixture was'allowed to come to room temperature (20 to 30 min.) then house vac.

8 (yield 48.5%) and 8.5 cc. (10.0 g.) of yellow residue.

The distillate was analyzed as follows:

Found Cale.

P 9. 4 9. as

15 insecticidal activity is shown by the following table. The

test was observed, to the concentration in weight percent of the toxicagent in the solvent at which, under standard test conditions, a 50%mortality of the insects in each test was observed.

Relative toxicity (toxicity index) While maintaining the LD of thestandard LD of a test sample In these tests dieldrin was used as astandard for tests against housefiies and-southern army worms. Parathionapplied for /2 hour at 50 followed by Hy-Vac (5 mm.) was employed as astandard with pea aphids, Mexican at for /2 hour. The mixture wasstirred and heated to and 43.5 cc. of (CH O) P was added at such a ratethat the temperature was maintained at -75 During /2 hr. of the additionheating was necessary.

bean beetle larvae and two-spotted spider mites. The quantity ofstandard employed to give 50% mortality of the insects in each test wasarbitrarily given a numerical value of 100. The toxicity of arepresentative product Aftercfinal addition heat was maintained at for 5of the invention aga the 60111111011 housefly (MHSCa .6 hour. Then housevac. was applied at same temperature for another 15 minutes. There wasobtained 15.0 g. of-CH Cl in the trap theory). The yellow oilwas'stripped at -10/10- and then distilled at 170 5 /10- mm. yielding92.0 g. (83.5% theory) a :1.5072, a residue of 10 cc. (12.0 g.) and 4.0cc. liquid in trap-colorless and having odor of (CH O) P. Sinceproductcontained chlorine, it was stripped at 35/10- mm. yielding 55.0 ml. ofstripped yellow oil and 13.0 ml. of colorless distillate n =1.5078.stripped oil was then distilled at -5 10" mm. Thus was obtained 43.0 cc.(54.0 g.) d 1.3 of colorless oil 40 made up by employing acetone or aneutral petroleum distillate lying within the kerosene range as asolvent. These solutions were tested for toxicity against insects listedin the table by spraying groups of plants infested with the insectsunder controlled conditions which varied 45 from test to test only inthe concentration of toxicant.

In the case of the two-spotted spider mites rotating preinfested beanplants were sprayed at low volume through a horizontal tunnel with watersolutions or suspensions of the toxicants by the method described byDorman and The 50 Hall (Journal Economic Entomology46; 151, 1953).

Mammalian toxicity tests were also conducted on male mice.

Relative toxicity of new compoun s [Toxicity index (standard=100)]Mexian Two- House Fly Pea Aphld Bean Southern spotted Toxicity CompoundName Dleldrin Parathion Bettle Armyworm Spider Male Mice,

V Larva Dieldrin 1 Mite Mg/Kg.

Parathlon 1 Parathion 1 Dimethyl 1-rnethyl-2-(phenoxy carbonyDvinylphosphate. 13.4 18 51 9 22 390 2-(benzyloxycarbonyD- l-methyb vinyldimethyl phosphate 18. 6 89 123 27 235 71 2-(p-MethoxyphenoxycarbonyD-1-methylvinyl dimethyl phosphate 18 17 61 22 39 101 Dlmethyll-methyl-Z-(p-tolyloxycarbonyDvinyl phosphate 13. 5 22 24 7 44 176Dimethyl l-methyl-Z-(phenethoxycarbonyDvinyl phosphate.-..- 6 73 64 9118 22 2-(p-methoxybenzyloxy-carbonyl) l-methylvinyl dimethyl phosphate15 21 68 8 121 116 Dimethylz-(alphaamethylbenzyloxycarbonyD-l-methylvinyl phosphate 20 95 136 26653 48 I-meth l-z-(z-phenoxyethoxycarbony )vinyl phosphate 9 13 73 17144 7. 8-15. 6

' standard.

- applied as a dust.

That the compounds of the present .inventiomexhibit a surprisingresidual toxicity when compared with Z-(methoxycarbonyl)-1-methylvinyldimethyl phosphate, is illustrated by testsconducted against .thebollweevil and twospotted mite. l 1 e The initial and residual .toxicityof each of .the compounds of the present invention-to boll weevils whensprayed at the rate of 0.5 .lb./acre on boll weevils caged on fieldtreated cotton plants .is shown in the following table. 2'-methoxycarbonyl.) .1 methylvinyl dimethylphosphate was found to be.ineifective two days after spraying whereas compoundsofthepresentinvention were found to possess significant insecticidal activity twodays after spraying.

Against the two-spotted mite pre-infested bean plants were heated withlow volume sprays of the test chemical at concentrations of 20 and 40times its LD /value, i.e., the amount by weight of test chemicaleifecting a 50% initial insect kill. mites were counted and expressed aspercent reduction from the check. The compounds of the present inventionwere superior to 2-methoxycarbonyl)-1-methylvinyl dimethyl phosphate inall recorded tests.

The compounds of this invention can be employed for insecticidalpurposes by the use of any of the methods which are conventionallyemployed in the art. For example, the compounds can either be sprayed orotherwise applied in the form of a solution or dispersion, or they canbe absorbed on an inert, finely divided solid and Useful solutions forapplications by spraying, brushing, dipping, and the like, can beprepared by using as the solvent any of the well-known inerthorticultural carriers, including neutral hydrocarbons such as keroseneand other light mineral oil distillates of intermediate viscosity andvolatility. Adjuvants, such as spreading or wetting agents, can also beincluded in the solutions, representative materials of this characterbeing fatty acid soaps, rosin salts, saponins, gelatine, casein, longchain fatty alcohols, alkyl aryl sulfonates, long-chain alkylsulfonates, phenol-ethylene oxide condensates, C to C amines andammonium salts, and the like. These solutions can be employed as such,or more preferably, they can be dispersed or emulsified in water and theresulting aqueous dispersion or emulsion applied as a spray. Solidcarrier materials which can be employed include: talc, bentonite, lime,gypsum, pyrophyllite and similar inert solid diluents. If desired, thecompounds of the present invention can be employed as aerosols, as bydispersing the same into the atmosphere by means of a compressed gas.

The concentration of the compounds to be used with the above carriers isdependent upon many factors, including the particular compound utilized,the carrier employed, the method and conditions of application, and theinsecticide species to be controlled, a proper consideration andresolution of these factors being within the skill of those versed inthe insecticide art. In general, however,

Seven days after spray, total living -the. compo unds of this inventionare eifective in concentrations of. from about 0.01% to 0.5% based uponthe total weight ,of the composition though under the same circumstancesas little as about 0.00001% or as much as 2% .or evenmoreof thevcompoundcan be employed with good results from an insecticidal standpoint.

When employed as an insecticide, a compound of this invention ,can beemployed either as the sole toxic .ingredientror theinsecticidalcomposition or it can be em- .ployedin conjunction with ,the otherinsecticidally-active materials. Representative insecticides of thislatter class include the naturally-occurring insecticides such aspyrethrum, rotenone, sabadilla, and the like, as well as the varioussynthetic insecticides, including DDT, benzene hexachloride,thiodiphenylamine, cyanides, tetraethyl pyrophosphate, diethylp-nitrophenyl thiophosphate, azobenzene, and the various compounds ofarsenic, lead, and/or fluorine.

Having thus described this invention in full what is desired to beprotected by United States Letters Patent is:

1. A compound of the general formula:

wherein R is selected from the group consisting of mononuclear arylhydrocarbon radicals, mononuclear aralkyl hydrocarbon radicals whereinthe alkyl moieties contain from 1 to 5 carbon atoms, and such aryl andaralkyl radicals substituted by a methoxy group, and R is an alkylradical containing from 1 to 5 carbon atoms.

2. Dialkyl 1-methyl-2-(aryloxycarbonyl)vinyl phosphate wherein each ofthe alkyl groups contains from 1 to 5 carbon atoms and the aromaticmoiety of the aryl group is the phenyl moiety.

3. Dialkyl l-methyl-Z-(aralkyloxycarbonyl)vinyl phosphate wherein eachof the alkyl groups and the alkyl moiety of the aralkyl group containsfrom 1 to 5 carbon atoms and the aromatic moiety of the aralkyl group isthe phenyl moiety.

4. Dimethyl 1-methyl-2-(phenoxycarbonyDvinyl phosphate.

5. 2-(benzyloxycarbonyl)-1-methyl-vinyl dimethyl phosphate.

6. 2-(p-methoxybenzyloxycarbonyl)-1-methylvinyl dimethyl phosphate.

7. 2-phenoxyethyl 3-(dimethoxy-phosphinyloxy)crotonate.

8. 2-(p-methoxyphenoxycarbonyl) 1 methylvinyl di-' methyl phosphate.

9. The method of combating insects which comprises applying to insecthabitats a compound of claim 1.

10. The method of combating insects which comprises applying to insectshabitats a compound of claim 2.

11. The method of combating insects which comprises applying toinsecthabitats a compound of claim 3.

12. The method of combating insects which comprises applying to insecthabitats dimethyl 1-methyl-2-(phenoxycarbonyl) -vinyl phosphate.

13. As an insecticidal composition of matter a compound of claim 1supported upon a finely divided inert carrier material, theconcentration of said compound being from about 0.00001 to about 2percent of the combined weights of said compound and said carriermaterial.

14. As an insecticidal composition of matter a compound of claim 1disseminated in an inert horticultural carrier liquid, the concentrationof said compound being from about 0.00001 to about 2 percent of thecombined weights of said compound and said carrier liquid.

15. Dimethyl 2-(alpha-methylbenzyloxycarbonyl) lmethylvinyl phosphate.

16. The method of combatting insects which comprises applying to insecthabitats a compound of claim 15.

2-(alpha-methylbenzyloxycarbonyl)-l-methylvinyl2-(alpha-methylbenzyloxycarbonyl)-1-methy1vinyl phosphate disseminatedin an inert horticultural carrier liquid, the concentration of saidphosphate being from about 0.00001 to about 2 percent of the combinedweights of said phosphate and said carrier liquid.

References Cited in the file of this patent,

UNITED STATES PATENTS Kosolapofi Jan, 8, 19,52 Whetstone Aug. 13, 1957Allen Dec. 10, 1957 Shapiro Mar. 11, 1958 Smith Apr. 8, 1958 HillyerJune 10, 1958 Watson July 8, 1958 Lorenz July 7, 1959 Stiles July 21,1959

1. A COMPOUND OF THE GENERAL FORMULA:
 9. THE METHOD OF COMBATING INSECTSWHICH COMPRISES APPLYING TO INSECT HABITATS A COMPOUND OF CLAIM 1.